Layered cracking catalyst and method of manufacture and use thereof

ABSTRACT

A layered catalyst contains a core of at least one, and preferably three, molecular sieve components within a shell layer of reduced molecular sieve content. A preferred catalyst consists of a core of a large pore molecular sieve, preferably a dealuminized Y-type zeolite, a shape selective paraffin cracking/isomerization component, preferably HZSM-5, and a shape selective aliphatic aromatization component, preferably gallium ZSM-5, within a shell of an alumina-rich, matrix. The shell can capture metals from the feeds being processed, it can act as a metals sink, and can remove metals from the unit by attrition. The catalyst is preferably prepared by forming the core and then coating or encapsulating the core with a shell having a reduced molecular sieve content. The shell may contain a pillared clay or other very large pore cracking component. The shell may be an attritable coating of an amorphous rare earth oxide, aluminum oxide and aluminum phosphate composite, which traps metals.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation in part of our prior co-pendingapplication U.S. Ser. No. 292,204, filed Dec. 30, 1988, and nowabandoned.

This application is also a continuation in part of our prior co-pendingapplication U.S. Ser. No. 335,068, filed Apr. 7, 1989, which is acontinuation-in-part of parent application U.S. Ser. No. 138,002 filedDec. 28, 1987, and now abandoned.

All of these related applications are incorporated herein by reference.

FIELD OF THE INVENTION

This invention relates to catalytic cracking of heavy hydrocarbon oilsto produce liquid hydrocarbons boiling in the gasoline and distillaterange.

BACKGROUND OF THE INVENTION

The present invention can best be understood in the context of itscontribution to conventional FCC processes. Accordingly, a briefdiscussion of conventional cracking processes and catalysts follows.

Conversion of heavy petroleum fractions to lighter products by catalyticcracking is well known in the refining industry. Fluidized CatalyticCracking (FCC) is particularly advantageous for that purpose. The heavyfeed contacts hot regenerated catalyst and is cracked to lighterproducts. Carbonaceous deposits form on the catalyst, therebydeactivating it. The deactivated (spent) catalyst is separated fromcracked products, stripped of strippable hydrocarbons and conducted to aregenerator, where coke is burned off the catalyst with air, therebyregenerating the catalyst. The regenerated catalyst is then recycled tothe reactor. The reactor-regenerator assembly are usually maintained inheat balance. Heat generated by burning the coke in the regeneratorprovides sufficient thermal energy for catalytic cracking in thereactor. Control of reactor conversion is usually achieved bycontrolling the flow of hot regenerated catalyst to the reactor tomaintain the desired reactor temperature.

In most modern FCC units, the hot regenerated catalyst is added to thefeed at the base of a riser reactor. The fluidization of the solidcatalyst particles may be promoted with a lift gas. Mixing andatomization of the feedstock may be promoted with steam, equal to 1-5 wt% of the hydrocarbon feed. Hot catalyst (650° C.⁺) from the regeneratoris mixed with preheated (150°-375° C.) charge stock. The catalystvaporizes and superheats the feed to the desired cracking temperatureusually the feed is cracked, and coke deposits on the catalyst. Thecoked catalyst and the cracked products exit the riser and enter asolid-gas separation system, e.g., a series of cyclones, at the top ofthe reactor vessel. The cracked products pass to product separation.Typically, the cracked hydrocarbon products are fractionated into aseries of products, including gas, gasoline, light gas oil, and heavycycle gas oil. Some heavy cycle gas oil may be recycled to the reactor.The bottoms product, a "slurry oil", is conventionally allowed tosettle. The catalyst rich solids portion of the settled product may berecycled to the reactor. The clarified slurry oil is a heavy product.

The "reactor vessel" into which the riser discharges primarily separatescatalyst from cracked products and unreacted hydrocarbons and permitscatalyst stripping.

Older FCC units use some or all dense bed cracking. Down flow operationis also possible, in which case catalyst and oil are added to the top ofa vertical tube, or "downer," with cracked products removed from thebottom of the downer. Moving bed analogs of the FCC process, such asThermofor Catalytic Cracking (TCC) are also known.

Further details of FCC processes can be found in: U.S. Pat. Nos.3,152,065 (Sharp et al); 3,261,776 (Banman et al); 3,654,140 (Griffel etal); 3,812,029 (Snyder); 4,093,537, 4,118,337, 4,118,338, 4,218,306(Gross et al); 4,444,722 (Owen); 4,459,203 (Beech et al); 4,639,308(Lee); 4,675,099, 4,681,743 (Skraba) as well as in Venuto et al, FluidCatalytic Cracking With Zeolite Catalysts, Marcel Dekker, Inc. (1979).The entire contents of these patents and publication are incorporatedherein by reference.

Conventional FCC catalysts usually contain finely divided acidiczeolites comprising, e.g., faujasites such as Rare Earth Y (REY),Dealuminized Y (DAY), Ultrastable Y (USY), Rare Earth ContainingUltrastable Y (RE-USY), and Ultrahydrophobic Y (UHP-Y).

Typically, FCC catalysts are fine particles having particle diametersranging from about 20 to 150 microns and an average diameter around60-80 microns.

Catalyst for use in moving bed catalytic cracking unit (e.g. TCC units)can be in the form of spheres, pills, beads, or extrudates, and can havea diameter ranging from 1 to 6 mm.

Although many advances have been made in both the catalytic crackingprocess, and in catalyst for use in the process, some problem areasremain.

The catalytic cracking process is excellent for converting heavyhydrocarbons to lighter hydrocarbons. Although this conversion is thewhole reason for performing catalytic cracking, the boiling range of thecracked product is frequently not optimum for maximum profitability.Usually the gasoline and fuel oil boiling range fractions are the mostvaluable materials. Light olefins (C₂ -C₁₀ olefins) are highly valuableonly if a refiner has a way to convert these olefins into gasolineboiling range materials via e.g. alkylation, or if these light olefinscan be used for their petrochemical value. Light paraffins, C₁₀ ⁻materials, are generally not as valuable because of their relatively lowoctane. The very light paraffins, particularly propane, usually are notas valuable as gasoline. There are ever more stringent limitations onthe allowable vapor pressure of gasoline, such that refiners can notblend as much light material into the gasoline as they would like to.Accordingly, there is great interest in converting "top of the barrel"components, or light hydrocarbons in the C₁₀ ⁻ boiling range, intoheavier products.

There is also a growing need in refineries to convert more of the"bottom of the barrel" or resid fractions into lighter components viacatalytic cracking. Many FCC units today add 5-15 wt % resid, ornon-distillable feed, to the catalytic cracking unit. Such heavymaterials in the past were never considered as suitable feeds forcatalytic cracking units, because of their high levels of ConradsonCarbon, sodium, and dehydrogenation metals such as nickel and vanadium.The market for resids (bunker fuel oil, road asphalt) is so limited thatrefiners have turned to FCC as one way to upgrade the value of the residfraction.

The most limiting factor in catalytic cracking of resids in conventionalFCC units appears to be metals deposition on the catalyst. The nickeland vanadium in the resid deposit almost stoichiometrically on the FCCcirculating catalyst inventory, leading to production of excessiveamounts of "dry gas" during catalytic cracking. This problem can beameliorated to some extent by adding metal passivators, such as antimonyand/or tin, to passivate the nickel and vanadium components deposited onthe catalyst due to processing of resid feed. Usually refiners are alsoforced to resort to very high levels of catalyst withdrawal andreplacement, to maintain the metals levels on the catalyst at atolerable level, and to maintain catalyst activity. This represents alarge daily expense (for make-up catalyst) and presents a disposalproblem because the spent catalyst has so much heavy metal on it.

Attempts have been made to modify catalytic cracking catalyst toaccommodate heavy feeds. It is known that commercially available FCCcatalysts with a high surface area, and an alumina rich matrix, are moreresistant to deactivation from metals contamination than other FCCcatalysts (Speronello, B. K. and Reagan, W. J., Oil and Gas Journal,Jan. 30, 1984, page 139). See also "Method Predicts Activity ofVanadium-Contaminated FCC Catalyst", E. L. Leuenberger, Oil and GasJournal, July 15, 1985, page 125.

Another approach to metals passivation is disclosed in U.S. Pat. No.4,372,841, incorporated herein by reference. Adding a hydrogen donormaterial to the reaction zone and passing catalyst through a reductionzone at high temperature at least partially passivates the catalyst.

Vanadium, when deposited on a catalyst, is fairly mobile and can migrateto zeolite sites, attack the zeolite and destroy it. This phenomenon wasdiscussed in "Metals Resistant FCC Catalyst Gets Field Test," Jars,Dalen, Oil and Gas Journal, Sept. 20, 1982, Page 135.

Although catalyst manufacturers are working on catalysts whichapparently can tolerate fairly high levels of metals, and thus permitconversion of more of the "bottom of the barrel" into light products,they have largely ignored the economically related problem of convertinglight materials, produced during cracking, into more valuable, heaviercomponents.

We have discovered a cracking catalyst, a method for manufacturing and acatalytic cracking process using this catalyst, which is metals tolerantand can, in a preferred embodiment, change the product distribution fromcatalytic cracking. We have discovered a way to efficiently convert, ina catalytic cracking unit, the "bottom of the barrel" into more valuableproducts, and in a preferred embodiment, also convert the relatively lowvalue "top of the barrel" materials (incidentally produced duringcracking) into more valuable products boiling in the gasoline range.

BRIEF SUMMARY OF THE INVENTION

Accordingly, the present invention provides a layered catalytic crackingcatalyst containing a core comprising at least 10 wt % of a large porecrystalline silicate and/or a large pore crystalline aluminophosphate,and/or a large pore crystalline silicoaluminophosphate, all of which arehereinafter referred to as large pore molecular sieves, and a shellcomprising less than 10 wt % large pore molecular sieves.

In another embodiment, the present invention provides a catalyticcracking catalyst comprising a core containing 10 to 95 wt. % percentmatrix material; 5 to 50 wt. % percent zeolite Y which optionally ispartially dealuminized, 0.1-20 wt. % HZSM-5; and 0.1-20 wt. % Ga/ZSM-5,and a shell of material containing less than 10 wt. % large poremolecular sieves and comprising at least 1 wt. % of the overall layeredcracking catalyst.

In a specialized embodiment, the present invention provides a catalyticcracking catalyst comprising a zeolite deficient shell comprising atleast 10 wt % of a coating of a porous refractory material selected fromthe group of a rare earth oxide, aluminum oxide and aluminum phosphatecomposite, a magnesia, alumina, aluminum phosphate composite and a tin(IV) oxide composite around a core cracking catalyst containing at least10 wt % rare earth Y zeolite in a matrix.

In another embodiment, the present invention provides a process forcatalytic cracking of a hydrocarbon feed boiling in the gas oil andheavier boiling range to lighter products by contact of the feed in acatalytic cracking reactor at catalytic cracking conditions with alayered cracking catalyst comprising a core containing at least 10 wt %large pore molecular sieves and a shell containing less than 10 wt %large pore molecular sieves.

In another embodiment, the present invention provides a method ofmanufacturing a layered catalytic cracking catalyst comprising forming acore containing at least 10 wt % large pore molecular sieves byconventional means, and forming a shell comprising at least 1 wt. % ofthe overall layered cracking catalyst and containing less than 10 wt. %of the large pore molecular sieves around the core by contacting thepre-formed core with a large pore molecular sieve deficient (relative tothe core) matrix and recovering a layered catalyst as a product.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic diagram of a conventional FCC reactor andregenerator.

DETAILED DESCRIPTION

FIG. 1 is a schematic flow diagram of an exemplary FCC unit. Feed ischarged to the bottom of the riser reactor 2 via inlet 4. Hotregenerated catalyst is added via conduit 14, equipped with a flowcontrol valve 16. A lift gas is introduced near the liquid and solidfeed inlets via conduit 18. The riser reactor is an elongated,cylindrical smooth-walled tube.

The feed vaporizes and forms a dilute phase suspension with the FCCcatalyst. The suspension passes up the riser, which generally gets widerto accommodate volumetric expansion. Cracked products and coked catalystmay pass into a solid-vapor separation means, such as a conventionalcyclone. Preferably, the riser has a deflector and a short residencetime stripper, as disclosed in U.S. Pat. No. 4,629,552 (Haddad and Owen)incorporated by reference. Another good design is the closed cyclonedesign disclosed in U.S. Pat. No. 4,749,471 (Kam et al) which isincorporated by reference. A means for stripping entrained hydrocarbonsfrom the catalyst is usually provided in the base of vessel 6. Neitherthis stripping section, nor the solid-gas separation equipment is shownin the drawing for clarity. Such equipment is conventional. Crackedproducts are withdrawn from the reactor by conduit 8.

Stripped catalyst containing coke is withdrawn via conduit 10 andcharged to regenerator 12. The catalyst is regenerated by contact withan oxygen-containing gas, usually air added via line 9. Flue gas iswithdrawn from the regenerator by line 11.

Usually the feed temperature is about 150° C. to 375° C. The regeneratorusually operates at about 650° C. to 750° C. and the catalyst to feedweight ratio is usually about 3:1 to 10:1, adjusted as necessary to holda reactor outlet of about 450° C. to 550° C.

Cracked product from the FCC unit passes from outlet 8 to mainfractionator 20, where product is separated into a heavy slurry oilstream 22, heavy distillate 24, light distillate 26, naphtha 28, and alight overhead stream 30, rich in C₂ -C₄ olefins, C₁ -C₄ saturates, andother light cracked gas components. This light stream is usually treatedin an unsaturated gas plant 32 to recover various light gas streams,including C₃ -C₄ LPG, and optionally C₂ - fuel gas or the like.

Preferably a light, H₂ rich gas stream is recycled from the gas plantvia line 34 for use as all, or part, of a lift gas used to contactcatalyst in the base of riser 2.

The catalyst and process of the present invention work very well in theconventional FCC units described above, and in TCC units. The maximumbenefit from the present invention is achieved when a heavy, metalscontaining residual feed is at least part of the feed to the catalyticcracking unit.

Feeds

Most FCC and TCC units crack gas oil or vacuum gas oil feeds, i.e.,those having an initial boiling point above 400°-500° F., and an endboiling point above 750°-850° F.

The feed can include any wholly or partly non-distillable fraction, e.g.650° C.+ boiling range material. Resids, deasphalted resids, tar sands,shale oils, coal liquids and similar heavy material, may be used as partor all of the feed.

Layered Catalyst

The catalysts used herein comprise a core containing at least one, andpreferably three molecular sieve components, inside a shell layer ofmolecular sieve deficient material. We may refer to these catalystshereafter as "layered" catalysts. The layered catalyst preferablycomprises a core containing at least 10 wt. % large pore molecularsieve, as hereafter defined, surrounded by a porous shell.

SHELL

The shell comprises a molecular sieve deficient layer on the outside ofthe catalyst. Preferably less than 10 wt. % large-pore molecular sievesor other crystalline or highly structured cracking components arepresent in the shell layer.

The shell can be a conventional matrix material, such as alumina orsilica-alumina. The function of the matrix in conventional catalyticcracking catalysts is well known. Briefly stated, the matrix protectsthe relatively soft and fragile molecular sieve components from physicaldamage. The matrix acts to some extent as a sodium sink, and minimizeslocalized high temperatures when burning coke from the molecular sieve.

In the present invention, the shell functions as a metals getter or sinkand may achieve some cracking of extremely large molecules. Preferably arelatively soft, highly porous alumina, is used. Metals tend to depositrapidly on such materials, and the gradual attrition of, e.g., thealumina permits metals to be removed from the unit with catalyst"fines".

The shell can thus perform, in a preferred embodiment, a dual role. Theshell first provides a place for metals in the feed to deposit. Thiskeeps Ni, V, etc, from the molecular sieve cracking components. Then themetals are removed with alumina, or other shell material, as "fines."Metals removal minimizes migration of metal, or formation of reactivespecies in the unit, such as pentavalent vanadium compounds in theregenerator.

Rather than remove the deposited metals by attrition, the metals canalso be immobilized. Incorporation of compounds which react with Ni, V,Na, Fe, or other deposited metals to form stable metal compounds isbeneficial. BaO, MgO, CaO, La₂ O₃, Ce₂ O₃ and similar alkaline and/orrare earth compounds form, e.g., stable vanadium compounds which neithermigrate by solid-solid interactions nor form volatile vanadium compoundsin the FCC regenerator.

The shell's second major role is conversion of extremely large moleculesfound in residual fractions. These large molecules can not fit readilyinto conventional large pore zeolites such as zeolite X or Y. Themolecular sieve deficient shell may not be as selective a crackingcatalyst as conventional zeolitic cracking catalysts, but only limitedconversion of very large molecules in the feed is necessary to renderthese large molecules down to a size where they can be cracked by largepore zeolites. Pillared layered clays would be very effective atconverting these very large molecules to ones capable of fitting intoconventional large pore zeolites.

CORE

The core comprises a large pore molecular sieve, preferably zeolite Y.The core preferably also contains both a shape selective paraffincracking/isomerization component, preferably HZSM-5 and a shapeselective aliphatic aromatization catalyst, preferably GaZSM-5.

Large Pore Cracking Component

The large-pore molecular sieve cracking component may be a conventionalzeolite. Some of these, and patents describing their preparation arediscussed hereinafter. Zeolite L, zeolite X, zeolite Y, and preferablyhigher silica forms of zeolite Y such as Dealuminized Y (DAY; U.S. Pat.No. 3,442,795), Ultrastable Y (USY; U.S. Pat. No. 3,449,070),Ultrahydrophobic Y (UHP-Y; U.S. Pat. Nos. 4,331,694, 4,401,556), andsimilar materials are preferred for use herein. Zeolite beta (U.S. Pat.No. 3,308,069) or Zeolite L (U.S. Pat. Nos. 3,216,789; 4,544,539;4,554,146 and 4,701,315) may also be used. These materials may besubjected to conventional treatments, such as impregnation or ionexchange with rare earths to increase stability. These patents areincorporated herein by reference.

These large-pore molecular sieves have a geometric pore opening of about7 angstroms in diameter. In current commercial practice, most of thecracking of large molecules in the feed is done using these large poremolecular sieves.

Very Large Pore Cracking Component

In addition to the large-pore cracking components described above whichhave found extensive use commercially, several recently developed verylarge-pore cracking components may also be used. All of these materialshave a geometric pore opening or portal greater than about 7 Angstromsin diameter.

VPI-5 is a molecular sieve with pore openings or portals larger thanabout 10 Angstrom units in diameter. It is an aluminophosphate typesieve with 18-membered rings of tetrahedrally-coordinated or T-atoms.Such molecular sieves have very large pore volumes, and extremely largepore openings. Such large pore sieves would be very useful for crackingthe very large molecules associated with high boiling or residualfractions. By contrast faujasites have portals containing 12 memberedrings. VPI-5 was described by M. Davis, C. Saldarriaga, C. Montes, andJ. Garces in a paper presented at "Innovations in Zeolite MaterialsScience" Meeting in Nieuwpoort, Belgium, Montes, J. Garces and C.Crowder, Nature 331, 698 (1988).

Pillared, interlayered clays may also be used as a large pore crackingcomponent. U.S. Pat. No. 4,742,033 discloses a pillared interlayeredclay. This patent is incorporated by reference.

U.S. Pat. No. 4,515,901 discloses forming an interlayered pillared clayby mixing a clay with a polar solvent, a soluble carbohydrate, and asoluble pillaring agent. The mixture is then heated to form theinterlayered pillared clay. Useful clays are smectites such asmontmorillonite.

In U.S. Pat. No. 4,367,163, pillars of silica are added to smectites toincrease the interplatelet distances. U.S. Pat. Nos. 4,515,901 and4,367,163 are incorporated herein by reference.

U.S. Pat. No. 4,757,041, which is incorporated herein by reference,discloses a class of pillared interlayered clay molecular sievesproducts with regularly interstratified mineral structure. Thesematerials are prepared by cross-linking interstratified mineral clay,and are reported to possess extraordinary thermal and hydrothermalstabilities.

U.S. Pat. No. 4,600,503 (Angevine et al), which is incorporated hereinby reference, discloses thermally stable layered metal oxides containinginterspathic polymeric oxides employed in hydrotreating catalyst used toupgrade residual oils. The layered materials disclosed in that patentmay be used as all of part of the "large pore" cracking component of thecatalyst of the present invention.

Published European patent application EP 0 284 278 A2 (Kirker et al),which is incorporated herein by reference, discloses hydrocracking aheavy feed containing polycyclic aromatics to form a lube based stock.The hydrocracking catalyst is a layered silicate such as magadiite whichcontains interspathic polymeric silica and interspathic polymeric oxidesof one or more of Al, B, Cr, Ga, In, Mo, Nb, Ni, Ti, Tl, W and Zr. Suchlayered silicates may be used as all or part of the large pore crackingcomponent of the present invention.

Published European Application EP 0 205 711 A2 (Chu et al), which inincorporated herein by reference, discloses layered oxides containinginterlayer polymeric oxides and their synthesis. Layered oxides of highthermal stability and surface area which contain interlayer polymericoxides such as polymeric silica are prepared by ion exchanging a layeredmetal oxide, such as layered titanium oxide, with organic cation tospread the layers apart. A compound, such as tetraethylorthosilicate,capable of forming a polymeric oxide, is thereafter introduced betweenthe layers. The resulting product is treated to form polymeric oxide,e.g., by hydrolysis to produce the layered oxide product. Such layeredmaterials may be as used all or part of the large pore crackingcomponent of the present invention.

U.S. Pat. No. 4,238,364 discloses the preparation of stabilizedpillared, interlayered clays. U.S. Pat. No. 4,665,220 discloses use ofthese clays as catalysts in reactions capable of catalysis by protons.The contents of both of these patents are incorporated herein byreference.

SAPO's, or silicon-substituted aluminophosphates, which have a threedimensional crystal framework of suitable size may also be used as thelarge pore cracking component. U.S. Pat. Nos. 4,440,871 and 4,741,892and 4,689,138, which are incorporated herein by reference, disclosesilicoalumino phosphate molecular sieves.

It should be emphasized that the process and catalyst of the presentinvention does not require the use of any single "large pore" crackingcomponent. The large pore cracking component may comprise mixtures ofone or more of the above materials, e.g., an equal mix of catalyticallyactive forms of RE-USY, VPI-5 and a pillared clay.

Expressed as Constraint Index, CI, the large pore cracking componentshould have a CI of less than 1 and preferably less than 0.8. Details ofthe Constraint Index test procedures are provided in J. Catalysis 67,218-222 (1981) and in U.S. Pat. No. 4,711,710 (Chen et al), both ofwhich are incorporated herein by reference.

SHAPE SELECTIVE COMPONENT

The preferred, but optional, shape selective paraffincracking/isomerization component can be any shape selective zeolitewhich at the conditions experienced in a catalytic cracking unitpromotes formation of olefinic and/or iso-olefinic materials. Anyzeolite having a Constraint Index of 1-12 can be used herein, but ZSM-5is especially preferred.

Preferred shape selective zeolites are exemplified by ZSM-5, ZSM-11,ZSM-12, ZSM-23, ZSM-35, ZSM-48, ZSM-57 and similar materials.

ZSM-5 is described in U.S. Pat. No. 3,702,886, U.S. Pat. No. Re. 29,948and in U.S. Pat. No. 4,061,724 (describing a high silica ZSM-5 as"silicalite").

ZSM-11 is described in U.S. Pat. No. 3,709,979.

ZSM-12 is described in U.S. Pat. No. 3,832,449.

ZSM-23 is described in U.S. Pat. No. 4,076,842.

ZSM-35 is described in U.S. Pat. No. 4,016,245.

ZSM-48 is described in U.S. Pat. No. 4,397,827.

ZSM-57 is described in U.S. Pat. No. 4,046,859.

These patents are incorporated herein by reference.

Zeolites in which some other framework element is present in partial ortotal substitution of aluminum can be advantageous. Elements which canbe substituted for part of all of the framework aluminum are boron,gallium, zirconium, titanium and trivalent metals which are heavier thanaluminum. Specific examples of such zeolites include ZSM-5 and zeolitebeta containing boron, gallium, zirconium and/or titanium. In lieu of,or in addition to, being incorporated into the zeolite framework, theseand other catalytically active elements can also be deposited upon thezeolite by any suitable procedure, e.g., impregnation.

Preferably, relatively high silica shape selective zeolites are used,i.e., with a silica/alumina ratio above 20/1, and more preferably with aratio of 70/1, 100/1, 500/1 or even higher.

Preferably, the shape selective paraffin cracking/isomerization zeoliteis placed in the hydrogen form by conventional means, such as exchangewith ammonia and subsequent calcination The zeolite may be used in anyform which promotes paraffin upgrading.

The preferred, but optional, shape selective aromatization component canbe any zeolite having a Constraint Index of 1-12 and additionalcomponents which promote paraffin aromatization at catalytic crackingconditions.

Gallium exchanged or impregnated ZSM-5 is especially preferred for useherein because of its ability to convert light paraffins such aspropanes and butanes into aromatic hydrocarbons which are valuable aspetrochemicals or as high octane gasoline blending components. Galliummay be incorporated into the zeolite framework during synthesis or itmay be exchanged or impregnated or otherwise incorporated into the ZSM-5after synthesis. Preferably 0.05 to 10, and most preferably 0.1 to 2.0wt. % gallium is associated with the aromatization zeolite.

On a matrix free basis, the relative ratios of the preferred threecomponent zeolite core can vary greatly, depending on feedstocks,products desired, and to a lesser extent on catalytic crackingconditions.

In general, the function of the large pore cracking components is bulkconversion of heavy feed or of cracked asphaltenes or other largecracked products to lighter materials, including light paraffins andlight olefins in the C₂ -C₁₀ range.

The light paraffins are not preferred products. The C₅ ⁺ paraffins tendto be relatively low in octane number. They can be upgraded byconventional means such as platinum reforming, but this increases costs.There is a significant yield loss during reforming, and reliance onreforming tends to increase the aromatics content of the gasoline pool.

The shape selective zeolite cracking/isomerization catalyst converts asignificant portion of these paraffins to olefins and iso-olefins, withhigher octane number, in the case of the C₅ ⁺ olefins, and morereactivity in the case of the C₄ ⁻ olefins.

The light olefins produced by the shape selective cracking/isomerizationcatalyst and by the large pore cracking catalyst can be easily upgradedin conventional alkylation units. In addition, the iso-olefins can beprocessed in etherification units to high octane oxygenates such as MTBEor TAME. By increasing the amount of shape selectivecracking/isomerization catalyst present in the layered catalyst, it ispossible to enhance the production of C₂ -C₁₀ olefins and, viasubsequent alkylation or etherification steps, increase gasoline yieldsand octane number, with aliphatic components rather than aromaticcomponents.

The shape selective aromatization zeolite converts C₁₀ ⁻ paraffins, andespecially C₄ ⁻ paraffins, to aromatics. The aromatics produced,primarily benzene, toluene, and xylene (BTX) are extremely valuable bothas petrochemicals and for use in enhancing the octane number of thegasoline pool.

Preferably the conventional, large pore cracking component is present inan amount roughly equal to four times the combined amount of shapeselective paraffin cracking/isomerization zeolite and shape selectiveparaffin aromatization zeolite. Thus, a catalyst whose core contains 80wt. % RE-USY zeolite, 10 wt. % HZSM-5 and 10 wt. % GaZSM-5 (all on amatrix free basis) will give very good results. Expressed as weightpercent of total catalyst, the layered catalyst would have the followingcomposition when the layered catalyst contains 25 wt. % total zeolite:

    ______________________________________                                                         Core     Shell                                                Overall           g     wt. %    g   wt. %                                   ______________________________________                                             Shell       50 wt. %                                                          Core:       50 wt. %                                                     1)   Matrix      20 wt. %  25  50     50  100                                 2)   Large-pore  20 wt. %      20     40                                           molecular sieve                                                          3)   HZSM-5      2.5 wt. %       2.5   5                                      4)   GaZSM-5     2.5 wt. %       2.5   5                                      ______________________________________                                    

Preferably the zeolite content comprises 10-50 wt. % of the finishedcatalyst, with the remainder being matrix or shell.

CATALYST MANUFACTURE Core

The core comprising one or more molecular sieves including, e.g.,zeolites, and some binder, must be prepared first.

The different zeolite components can be wet ball milled or dry blendedtogether, and then may be added to a suitable matrix, e.g. asilica-alumina gel, clay composite or an alumina-clay composite or asilica sol or other matrix such as an alumina rich sol and furthermixed. The matrix and zeolite mixture can be extruded, prilled,marumerized, tabletted, dropped in an oil bath, etc. to form relativelylarge particles. For use in fluidized bed catalytic cracking units thematrix-zeolite mixture is preferably spray dried, but any other meanscan be used to make a fluidizable catalyst particle, such as crushing orgrinding larger size extrudates or pills.

Layered Core

It is preferred, but not essential, to provide a layered core, with thelarge pore cracking component, such as zeolite Y, comprising theoutermost layer of the core. The inner portion of the core can containone or more of the shape selective, Constraint Index 1-12, zeolitecatalysts for paraffin cracking/isomerization and/or for aromatizationof aliphatics to aromatics.

In a preferred embodiment, the shape selective zeolite components, suchas HZSM-5 and GaZSM-5 are mixed together with a conventional binder suchas silica, or silica-alumina to form a first stage product. The firststage product should be then subjected to drying or calcination or othertreatment to fix it in a stable enough form to maintain its integrity orgreen strength in subsequent steps, wherein the large pore molecularsieve cracking component is added as an external layer to the shapeselective zeolite first stage product.

Shell

A shell can be added by taking the first stage product and spraying ontoit a slurry or gel shell containing a reduced content of large poremolecular sieve(s).

The shell can be added by any other means which will add a molecularsieve deficient layer to the core material described above. In the caseof an FCC catalyst, a spray dried core component can be sprayed with agel or slurry containing an aqueous slurry of inorganic solids such asclay, silica, alumina and silica-alumina gel.

A uniform impregnation of a large preformed particle should be avoided,what is sought is coating, not impregnation. A preferred coatingtechnique, and preferred equipment for carrying out the coating process,are discussed in Chapter 12 of Catalyst Manufacturer, A. B. Stiles,Marcel Dekker, Inc., 1983, which is incorporated herein by reference.The cores to be coated are placed in a rotating drum and a low zeolite"paint" is coated onto the core. The thickness of the paint layer iscontrolled by the amount of slurry which is coated on the cores. Tobuild up a thicker core, multiple coating runs can be completed, or thecoating apparatus, such as a Penwalt-F. J. Stokes coating pan, may beheated to permit continuous operation.

Yet another efficient way of adding a coating to the catalyst is thespherudizer. Spherudizing is a special technique of catalyst manufacturedeveloped by the Dravo Corporation. A disk rotates at an angle whilesmall spheres of a seed material (the core) are placed in the bottompart of the disk. A spray of a cohesive slurry (the "low zeolite" shell)is sprayed onto the smaller particles. A shell layer gradually forms andthe spheres increase in size. By careful control of the size of thestarting seeds, the rate of addition of the slurry shell material, andthe rate of rotation of the disk, coated particles of a desired size canbe obtained. Some experimentation may be necessary to determine theoptimum core/shell formulation and preparation techniques using thespherudizer. Such routine experimentation is common to the use of thespherudizer, and well within those skilled in the catalyst manufacturingarts.

Although we have referred above to a zeolite deficient "paint", itshould be emphasized that the "paint" may contain some zeolite content,and indeed preferably contains some large pore catalytic crackingcomponents which may be zeolitic in nature. The shell can, andpreferably does, have a dual role of protecting the inner shapeselective zeolite-rich core, and of bringing about a measure of crackingof the extremely large molecules associated with heavy feeds. To promotesome cracking of large molecules the paint may preferably contain somelarge pore zeolite, or most preferably contains some of the "large pore"zeolites as defined above, i.e., VPI 5, pillared clays, and/or some ofthe more conventional large pore zeolites such as X and Y.

Usually, economics will necessitate minimizing the zeolite content ofthe outer layer to protect to the maximum extent possible the zeolitecontent from the harsh environment encountered in the catalytic crackingreaction zone. A highly siliceous layer, just a few microns thick, willcause only a minimal change in diffusion distances necessary to effectcracking, while potentially reducing the vulnerability of the core ofthe layered catalyst to metals deposition from the crude.

The shell may frequently contain a minor amount of zeolite, because ofsloppiness in the manufacturing process. Zeolites are relativelyexpensive materials and fragile zeolites in the shell would rapidlydeactivate and be destroyed by metals and sodium in the feed. Thesezeolites will retain their crystrallinity and cracking activity muchlonger if they are maintained within the zeolite rich core, and for thatreason, zeolites are preferably absent from the shell.

METAL CONTROL

The catalyst and process of the present invention permit significantlyimproved control of metal deposition rates on catalytic crackingcatalysts as compared to prior art catalysts. The zeolite-rich core canbe effectively protected from metals attack by use of a metallophyllicor metal loving shell (such as alumina).

The operation can be best understood by discussing the use of an aluminabound, zeolite-rich core.

In this embodiment, a relatively soft, alumina shell is used. Suchmaterials have an extremely high affinity for metals such as nickel andvanadium which are usually present in residual feed stocks. The softmaterials are subject to fairly high attrition rates, so that the metalswill be rapidly captured by the alumina matrix and removed from the unitas catalyst "fines" as the soft alumina abrades or attrits during use.The shell functions in a manner similar to an ablative heat shield on are-entry vehicle, protecting the catalyst during repeated cycles throughthe cracking unit.

As the outer shell attrits, more and more of the molecular sieve richcore is exposed. Many of the molecular sieve components in the core havea low affinity for absorption of metals such as nickel and vanadium fromthe feed; however, they will deposit on the alumina rich shell of aneighboring un-attrited catalyst of the invention.

Use of a core matrix comprising a metal immobilizing compound, such asMgO, CaO, BaO, La₂ O₃, Ce₂ O₃ and similar alkaline and/or rare earthmaterials provides a further measure of protection. Any feed metals thatpenetrate the shell, or are deposited directly on the core because theshell is gone or damaged, will be neutralized by the core matrix if itcontains a metal immobilizing compound. Incorporation of such materialsin the shell is also beneficial, especially so when the shell is arelatively hard, durable material.

The core/shell catalyst of the present invention provides an efficientway of upgrading heavy, metals containing resids. The preferred,somewhat friable alumina shell material acts as a throw-away scavengerto preferentially absorb metals from the feed. These preferred catalystsare to some extent renewed during use by the gradual removal of thepreferred, relatively soft and readily attritable shell material.

Of course using a relatively soft alumina material results in greatercatalyst attrition and catalyst loss. This is not totally undesirable,in that it is much better for the unit to experience relatively highattrition losses (and relatively high metals removal) and have a makeupcatalyst rate which balances catalyst lost daily through attrition. Thisis more efficient use of the zeolite cracking catalyst for crackingresid than removing 1-2% or more, per day of the circulating catalystinventory to maintain metals contamination on the catalyst at atolerably low level and to keep the cracking catalyst activity at asufficiently high level to permit efficient cracking.

ATTRITING METAL TRAP COATING

In one embodiment of the present invention, the zeolite deficient shellcomprises a surface coating which attrits and traps metal. A shell whichis weakly bound to the catalyst, and attrits off during the catalyticcracking process to expose new sites of the coating. When the surfacecoating comprises at least one metal trapping component, it is possibleto immobilize metals in the feed to the cracking unit on the surfacecoating, and to remove the metals from the cracking unit as the coatingattrits off.

A preferred coating which acts in this way is a retractory porousmaterial which comprises rare earth oxide, aluminum oxide and aluminumphosphate. Preferably the rare earth oxide, aluminum oxide and aluminumphosphate are present in a weight ratio of from about 10:20:70 to about90:5:5. Such a coating is preferably sprayed or otherwise coated on thesurface, rather than impregnated.

Other suitable coating materials include magnesia-alumina-aluminumphosphate gels, and tin (IV) oxide gels.

An especially preferred embodiment comprises a coating of a gel ofmagnesia-alumina-aluminum phosphate (MAAP) or a gel oflanthana-alumina-aluminum phosphate (LAAP) on a core catalyst such as aconventional cracking catalyst comprising at least 10 and preferably 20wt % calcined REY in a silica-alumina-clay matrix.

Use of at least 2 wt % coating, based on the weight of the finishedcomposite, is preferred. Operation with 10 wt % of a coating, such asthe LAAP gel discussed above, should allow a majority of the vanadium ina typical cat cracker feed to be trapped on the catalyst surface.

More details regarding these preferred coatings are contained in ourprior co-pending application U.S. Ser. No. 335,068, filed Apr. 7, 1989,which has been incorporated by reference.

EXAMPLES OF CATALYST PREPARATION

A layered catalyst is prepared by coating a core which consists of acatalyst with a shell which consists of Al₂ O₃ -MgO cogel.

The core component is prepared according to the procedure describednext. 2400 gms of Davison Z-14US, 300 gms of NH ZSM-5, 300 gms ofGaZSM-5 (all weights on ignited basis), each in form of a 30% ballmilledslurry containing deagglomerated particles (95% 2 microns), are addedtogether with 1304 gms of 50% aluminum chlorhydrol (23% Al₂ O₃, 8% Cl,Reheis Co.) and 2700 gms of Kaolin clay (ignited basis, Georgia Kaolin)in a 15 gallon Nalgene container containing 5996 gms of DI water. Themixture is subjected to high shear conditions using a Cowles Dissolver(Morehouse Industries; Fullerton, Calif.) equipped with a 6.5" bladeturning at 700-800 rpm for 30 minutes to prepare a pre spray-dryerslurry. The solids content of the slurry is adjusted between 25-40%using additional DI water, as necessary. Also, the slurry pH is adjustedbetween 4.0-4.6 using 20% H or 50% NH₄ OH, as necessary. The slurry isthen spray-dried at 370° F. outlet temperature. The spray dryer(Komline-Sanderson; Peapack, N.J.) is operated at 5.5 psig air pressurewith 0.06" nozzle at 250 cc/minute feed rate using a Moyno feed pump(Springfield, Ohio). The spray dried particles are air calcined for 2hours at 1000° F. in a muffle furnace. Subsequently the catalyst isfirst column exchanged with 1.0NH₄ NO₃ solution followed by a slurryexchange using a solution containing 0.75% rare earth chlorides(prepared from 60% AR solution, Davison Specialty Chemicals). Bothexchanges are carried out @5/1, solution/catalyst weight ratio. Thecatalyst is next dried at 250° F. overnight before use. The nominalcatalyst composition is 40% RE-USY (Z-14US), 5% HZSM-5, 5% GaZSM-5 and50% matrix (10% alumina binder, 90% clay).

The shell component is first prepared in the precursor form as describednext. Reagent grade Al(NO₃)₃.9H₂ O (1985.0 gms) is dissolved in 10000gms of DI water. Separately Mg(NO₃)₂.6H₂ O (192.0 gms) is dissolved in10000 gms of DI water. The solutions are combined and neutralized with20% NH₄ OH while vigorously stirring to a final value of 9.0 pH over aperiod of 30 minutes. The resultant gel is filtered and reslurried to 5%solids and homogenized for 5 minutes just prior to its use as describednext.

Using Yamato Model GA-21 Fluidized Bed Spray Granulator Dryer, 200 gmsof the shell precursor is sprayed into a heated (200° C.) fluid bed of190 gms. of the core component to prepare the layered catalyst.Additional batches of the layered catalyst are prepared in the samemanner.

ILLUSTRATIVE EMBODIMENT

The following illustrative embodiment does not represent an actualexperiment. It is an estimate, but one based on much other experimentalwork.

The illustrative embodiment is an estimate of the yields obtainable in aconventional FCC unit charging the same feed, at the same conditions,and changing only the catalyst compositions.

I. (Prior Art) The conventional catalyst represents a conventional largepore zeolite based cracking catalyst in a matrix. No ZSM-5 is present.

II. (Prior Art) Represents a conventional cracking catalyst plus 2.0 wt% HZSM-5.

III. Represents yields obtainable from a catalyst containing a bulkconversion component, e.g., USY and containing 1.0 wt. % GaZSM-5 and 1.0wt. % HZSM-5. The GaZSM-5 and HZSM-5 are present in equimolar amounts.The GaZSM-5 contains 1 wt % Ga in the ZSM-5 framework.

IV. Represents a catalyst with the GaZSM-5 and HZSM-5 present in aseparate particle, encapsulated in an alumina matrix.

    ______________________________________                                                                              Con. &                                                                        GaZSM/                                                                Conv. & ZSM-5 &                                           Conv.      Conv. +  GaZSM-5 Alumina                                           (No ZSM-5) ZSM-5    & ZSM-5 Matrix                                  % of FF   I          II       III     IV                                      ______________________________________                                        Gasoline  51.1       49.5     49.7    49.7                                    Paraffins 22.7       21       21      21                                      Olefins                                                                       C.sub.6.sup.-                                                                            3.8        4.5      4.0     4.0                                    C.sub.7.sup.+                                                                           10.6       10.0     10.0    10.0                                    Aromatics  8.5        8.5      9.2     9.2                                    Naphthenes                                                                               5.5        5.5      5.5     5.5                                    LCO       16         16       16      16.8                                    HCO       8           8.0     8        7.0                                    C.sub.3 .sup.= +C.sub.4 .sup.=                                                           8.7       10.3     10.1    10.1                                    C.sub.2.sup.-                                                                            3.5        3.5      3.5     3.5                                    Gasoline Composition                                                          Paraffins 44.5       42.5     42.5    42.5                                    Olefins   28.0       29.5     28      28                                      Naphthenes                                                                              11         11       11      11                                      Aromatics 16.5       17       18.5    18.5                                    Gasoline Octane No.                                                           Research Clear                                                                          92.6       93.6     94.0    94.0                                    ______________________________________                                    

We claim:
 1. A layered catalytic cracking catalyst having a core comprising at least 10 wt. % of at least 1 molecular sieve having a portal comprised of at most a 12 membered ring and a shell with a reduced content of said molecular sieve, relative to said molecular sieve's concentration in said core.
 2. The catalyst of claim 1 wherein the core comprises at least 1 molecular sieve having a portal comprising a 12-membered ring.
 3. The catalyst of claim 2 wherein the molecular sieve having a portal comprising a 12-membered ring is selected from the group of zeolite L, zeolite X, zeolite Y, Dealuminized Y, Ultrastable Y and Ultrahydrophobic Y.
 4. The catalyst of claim 3 containing at least one rare earth element.
 5. The catalyst of claim 1 wherein the core also comprises at least 10 wt. % of a molecular sieve having an effective pore opening greater than about 10 angstrom units.
 6. The catalyst of claim 1 wherein the core also contains at least one of VPI-5 and pillared, layered clays.
 7. The process of claim 1 wherein the core comprises zeolite beta.
 8. The catalyst of claim 1 wherein the core comprises at least one molecular sieve having a Constraint Index of 1-12.
 9. The catalyst of claim 1 wherein the core contains 0.1 to 25 wt. % of at least one of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-48 and ZSM-57.
 10. The catalyst of claim 1 wherein the core contains 0.1 to 20 wt. % of a molecular sieve having a Constraint Index of 1-12 and paraffin cracking/isomerization activity.
 11. The catalyst of claim 1 wherein the core contains 0.1 to 20 wt. % of a molecular sieve having a Constraint Index of 1-12 and paraffin aromatization activity.
 12. The catalyst of claim 1 wherein the core comprises 0.1 to 20 wt. % of a molecular sieve having a Constraint Index of 1-12, and said molecular sieve contains 0.05 to 10 wt. % gallium on an elemental metal basis.
 13. The catalyst of claim 1 wherein the shell comprises 60-90 percent alumina.
 14. The catalyst of claim 1 wherein the core comprises 50-99 weight % of the layered cracking catalyst and the shell comprises 50-1 weight %.
 15. The catalyst of claim 1 wherein the shell is essentially free of molecular sieves having portal comprising a 12 or less membered ring.
 16. The catalyst of claim 1 wherein the shell comprises at least 1 wt % of magnesium, barium, calcium, lanthanum, cerium, and compounds thereof.
 17. The catalyst of claim 1 wherein the average particle diameter of the layered catalyst is about 80 microns, the shell comprises at least 10 weight % of the layered catalyst, and the shell has a porosity, density, and hardness such that a majority of the shell will be removed by abrasion and attrition within 20 days of use in a fluidized catalytic cracking unit.
 18. The catalyst of claim 17 wherein a majority of the shell is removed within 5 days of use.
 19. The catalyst of claim 1 wherein the core comprises:(i) 5-50 wt. % large pore molecular sieve; (ii) 0.1-20 wt. % shape selective zeolite having paraffin cracking/isomerization activity; (iii) 0.1-20 wt. % shape selective zeolite having paraffin aromatization activity; (iv) 10-95 wt. % matrix material.
 20. The catalyst of claim 19 wherein the core comprises an inner core containing a majority of the shape selective zeolites having a Constraint Index of 1-12 and an outer core containing a majority of the large pore molecular sieves.
 21. A catalytic cracking catalyst containing a core and a shell, said core comprising:(i) 10-95 wt. % percent matrix material; (ii) 5-50 wt. % percent zeolite Y; (iii) 0.1-20 wt. % HZSM-5; (iv) 0.1-20 wt. % GaZSM-5;said shell comprising at least 1 weight % of the overall cracking catalyst and containing less than 10 wt % molecular sieves.
 22. A method of manufacturing a layered catalytic cracking catalyst comprising;a) forming a core comprising at least 10 wt. % large pore molecular sieve component by conventional means, and b) forming a shell comprising at least 1 wt. % of the overall catalyst and containing less than 10 wt % large pore molecular sieve around the core by contacting the pre-formed core with a molecular sieve deficient matrix, relative to the core matrix, and recovering a layered catalyst as a product.
 23. The method of claim 22 wherein the core comprises at least 10 wt. % large pore molecular sieve, and at least 1 wt. % ZSM-5.
 24. The catalyst of claim 1 wherein the zeolite deficient shell comprises at least 10 wt % of a coating comprising a refractory porous material selected from the group of:a) a rare earth oxide, aluminum oxide and aluminum phosphate composite; b) a magnesia, alumina, aluminum phosphate composite; and c) a tin (IV) oxide composite; andthe core comprises a cracking catalyst containing at least 10 wt % of rare earth Y zeolite in a matrix comprising silica and alumina. 